JPS63241859A - Thin film electrode supported on electron conducting sheet and manufacture thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a supported thin film lithium electrode and a method for manufacturing the same. More particularly, the present invention relates to thin film electrodes of lithium, lithium alloys, or foreign lithium supported on sheets of electronically conductive material, and methods of making the same.

[Prior art and problems to be solved by the invention] Rechargeable lithium generator (or lithium battery) (Burnab, British Columbia, Canada)
y), Molt Energy Limited) appeared on the market, and since the more recent advent of polymer electrolytes,
Along with the development of lithium generators, solid state batteries have all advanced very rapidly in the last few years. All of these new systems use thin film techniques that require low current densities, making the lithium electrode extremely easy to redeposit and repeatedly use. Due to this trend, it is increasingly necessary to produce lithium electrodes in the form of thinner membranes, which are approximately 100μ for liquid electrolyte batteries and approximately 1μ or more and less than 30μ for polymer electrolytes.

A thin lithium film having a thickness of about 100 microns can be used and handled relatively easily. Commercially produced thin films are available at prices in the order of $100 per bond. However, manufacturing thinner membranes requires extrusion and then lamination, which quickly increases costs. The latter operation is time consuming and difficult (and therefore expensive);
As a result, the production cost of this lithium is at least 3
Double. Considering that the manufacturing cost of lithium occupies a non-negligible portion of the price of a battery, the manufacturing cost could account for up to 50% of the price. Very thin membranes (50μ) are not only more expensive, but also difficult to handle. This is because lithium thin films are highly malleable and easily adhere to many common materials. This means that lithium thin films are extremely difficult to handle in the continuous process of assembling batteries with stacked membranes consisting of electrode (+)/electrolyte/lithium electrode.

The technology used in the manufacture of polymer electrolyte lithium batteries, which is of particular interest in the present invention, is particularly required in this regard.

The reason is that regarding the currently known properties of electrolytes,
This is because the required thickness of the lithium film is between 30 and about 1 micron. Ways to overcome this difficulty are known, for example by using double-sided negative electrodes, which are twice as thick as required. (3rd International Conference on Lithium Batteries, May 27-30, 1986, Kyoto, Japan, Abstracts #ST-11). However, its purpose is Li/electrolyte/(+)/Ni/Lf
/Electrolyte/ (+)/Ni/Li,,,, (+)/
If we were to make bipolar batteries lined with Ni (although Nf was chosen here as an example), we would need to rely on extremely thin films to avoid excess lithium. . Excess lithium is actually detrimental to raw material costs and storage energy density (especially when expressed as energy per unit volume). Furthermore, in the case of batteries designed for room temperature operation, the amount of lithium required is extremely small (1-2C/clD''), and when corresponding to thicknesses of 1-5μ, the above-mentioned excess becomes decisive.

Various methods have been suggested for the production of ultra-thin films of lithium, for example for use in coating metal collectors. Examples include the production of thin films of lithium using heated evaporation, sputtering, or electron beams. However, these techniques are relatively time-consuming and expensive, as they are performed under high vacuum and strictly dust-free conditions. Thin films with a thickness of less than 1 μm are obtained in this way.

There are other methods, such as laminating and depositing on a metal support: U.S. Pat. No. 3,756,789, 1
September 4, 1973 1 Inventor Alder and No. 3721113; March 1973 1 Inventor Houseplan or method of hot coextrusion with plastic materials (European Patent Application No. 0 148 241; Park and others
June 26, 1985, and No. 0145498, Cook et al., June 19, 1985);
All of these methods have serious deficiencies, particularly when applied to the manufacture of rechargeable polymer electrolyte cells.

On the other hand, there is a method of spreading a steel plate in a zinc plate and plating it. In this regard, the following patents may be cited as references: Japanese Patent Application No. 57-203758 Nippon Steel Japan Patent Application No. 57-203759 Japan Patent Application No. 57
-2037fiQ No. 〃British patent 208034
G77 Canadian Patent 114521 (1 Battelle Memorial Institute)
lle Memorial In5tituto
) The techniques disclosed in these patents obviously cannot be used to create thin layers of lithium on metal plates. Mention must also be made of electroplating with a roller on one side of a steel plate according to a method of Nippon Steel ("New Factory", December 1986).

When used in batteries, controlling the thickness of the lithium film is even more important than in plating methods. On the other hand, if the lithium layer is too thin, part of the collector will be exposed during discharge, which can lead to irreversible or even serious problems during recharging. However, when lithium is deposited, it is not deposited on a metal collector (e.g. nickel), but when it is re-deposited on lithium itself, it can be deposited repeatedly many times (more than 500 times). It is absolutely necessary to control the thickness throughout the battery manufacturing process so that it is not too thick, as too thick is bad for cost and energy storage.Finally, the electrodes when the batteries are connected in series It is necessary to control the thickness to ensure that the surface capacitance (C7cm2) of the battery is balanced. If not, the capacitance may change differently between individual cells during repeated use. Probably.

The present invention overcomes the above-mentioned difficulties in using lithium electrodes of various thicknesses, e.g.
The intention is to produce lithium membranes quickly, economically and particularly reproducibly from batch to batch.

The present invention also seeks to take advantage of the excellent wetting properties of molten lithium, lithium alloys, and multi-metal lithium when used with metals such as nickel and copper.

One of the objects of the present invention is to apply a thin lithium film (approximately 1 to 20 μm
The purpose of the present invention is to develop a rapid method for producing lithium-deposited rolls by utilizing the high-speed wetting properties of lithium-ionized materials (with a thickness of 100%).

Another object of the present invention is to take advantage of the high speed of the method to shorten the contact time between the molten lithium and the support object, thereby reducing the likelihood of chemical or thermal attack by the molten lithium. .

One object of the present invention is to subject the lithium to a heat treatment by controlling the equipment used and the speed at which the rolls of suitably prepared metal sheets are unrolled. Examples include controlling solidification (lithium microcrystalline) rates or chemical processing rates.

Another object of the present invention is to produce a supported lithium electrode developed for polymer electrolyte batteries that has molten lithium deposited in a manner that allows the thickness of the deposited lithium to be tightly controlled.

One objective of the present invention is to ensure that thin and reproducible deposits are obtained by controlling the thickness of the lithium layer and hence the capacitance. On the one hand, it would be possible in this way to avoid overusing lithium, and on the other hand, it would be possible to ensure reliable electrochemical operation during repeated use of the lithium electrode and battery.

[Means for Solving the Problems] In a broad sense, the present invention is a method for manufacturing a thin film electrode, which is made from any one of lithium, lithium alloy, and lithium mixed with foreign substances, and whose melting point is 50° C. or higher, which is the melting point of lithium. The present invention relates to a manufacturing method in which a thin film electrode supported on an electronically conductive sheet having a constant thickness is wound into a roll, and the sheet is manufactured from a source of the above-mentioned raw metal. According to the method of the present invention, a molten metal bath of this raw metal is prepared, the sheet is continuously spread out, and a certain amount of the raw metal in a molten state is applied to at least one of two sides of the sheet in an inert atmosphere. It is applied continuously onto the surface to form a film on the sheet. The thickness of the film is constant from about 0.1 to about 40μ, and its surface is uniform and uniform.

Appropriate methods must be used to prevent the molten raw metal from solidifying upon contact with the sheet and to control the solidification of the raw metal on the sheet after the film has been formed on the sheet. Apparently, this method is also suitable for producing collectors coated on both sides with lithium. For example, the method of the present invention can be applied to a sheet that does not accept lithium, on which a positive electrode material or a positive electrode material is covered in advance with an electrolyte, or on which a film of lithium, lithium alloy, or lithium mixed with a foreign substance is applied. It can be used to form.

In preferred embodiments of the invention, the sheet is made of metal, metal alloy, metallized glass fiber, or metallized or charged plastic. Preferred metals are copper, nickel, iron, or sorybdenum. When choosing an alloy, choose a nickel, copper, or iron-based alloy, such as bronze, copper alloy, or steel. For practical purposes, a nickel sheet is preferable.

Regarding the melting material metal, it is metallic lithium or a compound or alloy with a high lithium content whose melting point is close to that of lithium, ±50°C, such as antimony, bismuth, boron, tin, silicon. , or an alloy of magnesium and lithium, or an alloy of magnesium and lithium mixed with lithium as a foreign substance.

According to another preferred embodiment of the invention, the sheet is unrolled over the molten lithium bath, with the bath temperature maintained at a temperature between the melting point of lithium and about 400°C. moreover,
According to another preferred embodiment of the invention, a molten lithium applicator is continuously rotated in the bath to apply molten lithium to the surface of a sheet of, for example, nickel. A desirable structure for the applicator is one in which there is a roller whose axis is parallel to the surface of the molten lithium, the bottom of the roller is immersed in the molten lithium, and the top is in contact with the surface of the sheet. The surface of the roller is rough and is always covered with lithium, lithium alloys, and molten lithium mixed with foreign substances.
This is applied uniformly to the surface of the above-mentioned nickel sheet, for example, to a constant thickness.

This rough surface can be of any type, but preferably consists of a regular geometric pattern. The pattern forms regularly spread depressions over the entire surface of the roller, where the molten material is collected and transferred onto the metal sheet.

The speed of unraveling the sheet is about 0.5 or IQOc
m/s is desirable. Additionally, in some situations, the rollers may be heated to prevent the molten lithium (pure, adulterated, or alloyed) from solidifying before it reaches the surface of the sheet to be coated. It is also possible.

In other embodiments of the invention, the sheet is heat treated before and/or after the base metal is deposited on the surface of the sheet.

In another embodiment of the invention, a scraper is provided;
Excess molten material on the surface of the roller is scraped off before it is transferred to the surface of the metal sheet to be coated.

In another embodiment of the invention, after the metal sheet has been coated with molten pure, alloyed, or adulterated lithium, the surface is treated with a scraper to remove the surface left by the rollers. Smoothing out imperfections.

It is desirable to maintain an inert atmosphere surrounding the lithium bath, both the lithium bath and the sheet, free of oxygen and water to prevent unwanted reactions.

Obviously, the apparatus can be modified to coat both sides of the metal collector if desired, as will be apparent to those skilled in the art. In another broad interpretation, the invention relates to a supported thin film electrode consisting of an electronically conductive sheet, at least in part selected from lithium, lithium alloys, and foreign lithium. It is coated with a layer of raw metal, and the raw metal layer has a uniform thickness of about 0.1 to 40 microns. The surface of this layer is practically smooth and cannot be removed with a knife.

The electronically conductive sheet is composed of metals, alloys, metallized glass fibers, or charged or metallized plastics. For example, copper, nickel, iron, and molybdenum, or alloys containing nickel, copper, iron,
Examples include brass, bronze, steel, and Monel alloy.

Preferably, this sheet is nickel.

The coating is preferably metallic lithium, but it may also be a compound or alloy with a high lithium content and a melting point close to that of lithium (±50°C).
Examples include antimony, bismuth, boron, tin, silicon, an alloy of magnesium and lithium, or lithium mixed with these as foreign substances.

[Example] Next, the present invention will be described using the attached drawings, but these drawings are shown by way of example and do not limit the present invention in any way.

The apparatus shown schematically in FIG. 1 has a spool 1 for supplying a metallized or metal sheet 3. The device shown schematically in FIG.

A take-up spool 5 is provided to take up the processed sheet, and takes up the sheet while the processing described below is being performed. This device also has bath 7
It contains molten lithium 9.

A heating element 11 and a thermal insulator 13 are provided to ensure that the lithium 9 is in a molten state and its temperature is maintained at a controlled temperature. This heating element is of course connected to an alternating current power supply in the usual manner. Finally, in the area schematically illustrated at 17, the bath and the sheet 3 being processed are
are maintained under a controlled atmosphere in which oxygen, water vapor, and other gases that might react with the lithium are removed. Area 3 is completely conventional and does not form any part of this invention.

A roller 1 with a textured surface serves as a coating device for attaching a thin film 3' of molten lithium to the lower surface of the metal sheet 3.
9, and the pattern on its surface acts as a capillary so that lithium adheres to the bottom surface of the sheet 3.The roller 19, which has a textured surface, also has a roller 19 for properly controlling the temperature of the lithium adhering to its surface. A normal heater 21 is provided. Additionally, if necessary, a scraper 22 (indicated by dotted lines in Figure 1) may be provided to remove excess melt from the surface of the roller before it is applied as a coating to the metal sheet surface 3. Can be removed.

Two wooden rods 2 and 2a are applied to the upper surface of the metal sheet 3 so that the contact angle between the sheet 3 and the roller 19 can be adjusted so that the metal sheet 3 and the roller 19 come into proper contact. Before the metal sheet 3 reaches the molten lithium, a temperature regulator 23 is installed to adjust the temperature of the sheet as it reaches the molten lithium bath. Similarly, another temperature regulator 25 is provided to adjust the heating or cooling of the lithium coated sheet before it is wound onto the spool 5.

One variant of this device, represented schematically in FIG. 1, is shown in FIG. Among them, the parts that are common to the apparatus shown in FIG. I can see you there.

Roller 27 is equipped with a heater 29 to maintain the appropriate temperature while processing the sheet.

Turning now to FIG. 3, the device shown in FIG.
I see that there is 1. This serves to reduce the thickness of the membrane and/or eliminate imperfections in the membrane created by rollers 19. The additional equipment must be kept at a sufficiently high temperature to ensure that the excess scraped material is returned to the bath in liquid form. This can be achieved by attaching a commonly used heating mechanism to the photographing device 31 (although not shown). Further, a presser roller 33 is placed directly above the scraper 31 so that the scraped surface is completely uniform. The uniform surface of the lithium-coated sheet is illustrated at 35. Heating the scraper is particularly useful when the initially deposited lithium film is thick, since the markings on the rollers can leave marks on the cooled lithium. The heated scraper 33 can eliminate such surface imperfections.

The product obtained according to the invention is used to manufacture the battery illustrated in FIG. This cell has a copper collector 37 with a thickness of 10μ. The thickness of the lithium layer 39 obtained by the operation of the invention is approximately 20 microns. This battery also includes a polymer electrolyte 41 with a thickness of 20μ and a positive electrode 43 with a thickness of 40μ.
and a copper collector 45 with a thickness of 10μ, for a total of 10
It has a thickness of 0μ.

An example of a metal sheet coated with band-shaped lithium is given in Section 5.6.
and 7. In FIG. 5, metallic lithium 49 is applied onto the metal sheet 47. In FIG. The beginning of the lithium band is indicated in the figure as 51, and the two uncovered parts of the band are designated by reference numerals 53 and 55. If it is desired to coat the nickel sheet with a repeating pattern of lithium, an application roller 19 can be used to create the repeating pattern 57. It is clear that instead of the pattern shown in FIG. 6, other patterns can also be used, such as the one shown at 5.9 in FIG. 7, for example.

The invention will now be illustrated by the following examples, which are not intended to limit the invention to these examples.

A spool of a thick JLfL electrolytic copper sheet (width: 7.6 cm, thickness: 25 μm) was used to fabricate a lithium electrode. The equipment chosen is the one illustrated in Figure 1, which includes a glove box (
The water content was 10 ppm or less, and the oxygen content was 10 pp+w or less. The sheet was placed as shown in Figure 1, and the unrolled sheet was unrolled and spread out by rotating a pulling roller at a speed of 2 cm/s. Stainless steel coating roller (width 7cm)
) was placed in the center of the copper sheet. The diameter of the roller is 2.5c
m, and its surface pattern is characterized by the characteristics of its surface pattern.
According to the description of ROTO Inc.), the number of dots is 200, the depth of the notch is 24 ohm, the volume is -5.0 with a pyramidal pattern. The temperature of the lithium bath is maintained at 260°C during the test.

Approximately 30% of the roller's volume is submerged in liquid. A stainless steel container measuring 10x5x2c+a contains approximately 50cc of "battery" grade lithium. 1
The 1st section board (23, 25) was not used in this test.
Approximately 10 m of lithium film is thus created on the copper and wound onto a winding roller.

The lithium thus obtained has no defects on the surface (O, S
μ or less) It also has a highly metallic appearance. The edges of the lithium on the steel are straight and not jagged.

The lithium thickness is very regular with an average of 5μ, varying less than 0.5μ in any direction.

The amount of lithium used was about 3cc to make a thickness of 5μ.

Continuous operation may produce large amounts of lithium, and it is sufficient to periodically add fresh lithium to the vessel.

The same equipment as in Example 1 was used to perform this example, except that an "inking" roller was used, the surface pattern was somewhat emphasized, and the number of strokes was 25. The depth of the notches is 330 ohms, the volume is 72, and the pattern is also pyramidal. Experimental conditions are the same, speed = 2
cm/s, and the bath temperature was -260°C. The thickness of the lithium thus formed on the steel is on average 8 μm, which corresponds to a consumption of 7 cclOm of lithium or 14 A,h of electricity. The bath and its immediate surroundings are kept in a helium atmosphere, and the take-up spool is kept in dry air (70
Wrap in an atmosphere with a dew point of 125°C or less).

Using the device shown in Figure 1, the speed at which the sheet is unraveled is 5.
double the speed (approximately 10 cm/s), and heat the nickel sheet (width 7 cm, thickness 8 μ) to 300 cm in advance using the temperature controller 23.
The same thickness of lithium was obtained by heating the "inking" spool to 300°C and operating the bath 9 at a temperature of 260°C.

A small helium jet was used at position 25 to cool the lithium-coated nickel before it reached the take-up spool.

15■1 A small battery (4cm") using the lithium produced in Example 1
) was configured. A 4 cm' disc was punched from the product of Example 1. On this lithium disk,
20/1 polyethylene oxide and lithium perchlorate
An electrolyte membrane having a thickness of 75 μm was deposited from a mixture having a ratio of .

A positive electrode based on nickel copolymer and TiS on a rectifier with a surface capacitance of 1.5 C/cm was fabricated on top of the above half cell.The temperature of the cell thus constructed was set to 80
When raised to 10 °C, the battery cools down to 10
It could be reused 0 or more times.

For example, polyethylene oxide can be used in Canadian Patent No. 4798.
No. 62, April 23, 1985, the dendrites were replaced with a 50μ thick synthetic copolymer and subjected to 50 strong discharge and charge cycles using an electrolyte with a conductor. There was no problem, and there was no sign that the lithium electrode was malfunctioning.

Another 4 cm2 cell was fabricated with a copolymer-based electrolyte using the lithium electrode prepared according to Example 2. As the positive electrode, a high capacitance ('5 C/cm2) was used.
) V6O13 was used. Lithium 10μ (i.e. 7
．． 3C/cm2), it means about 50% lithium for the positive electrode, but at 60°C 75%
It withstood repeated use under harsh conditions and did not produce dendrites or other phenomena that could lead to malfunction of lithium electrodes.

Medical JL
Seventeen unit cells each having a voltage of about 3.5V were integrated in series to produce one battery with a voltage exceeding 50V.

In this example, the positive electrode was made of MnO, and the electrolyte was copolymer-based as described above. The main feature of the finished product is that the battery is exceptionally thin, with a thickness of less than 1/3 inch.

[Brief explanation of the drawing]

FIG. 1 is a schematic illustration of an apparatus for carrying out an operation according to the present invention, FIG. 2 is a schematic illustration of another apparatus for carrying out the same operation, and FIG. Second
Fig. 4 is a cross-sectional view of a battery equipped with an anode according to the present invention, and Fig. 5 shows a metal sheet covered with a strip of lithium from above. Figure 6 is another view from above of a metal sheet with a repeating figure, and Figure 7 is another view from above of a metal sheet with another repeating figure. be. 1... Spool, 3... Sheet, 3'.
... Thin film of molten lithium, 5... Winding spool, )... Bath, 9... Lithium, 11... Heating element, 13... Thermal insulator, 19-... Roller, 21... ... Heater, 22 ... Scraping machine, 23.25 ... Temperature regulator, 27 ... Roller, 29 ... Heater, 31
...Scraper, 33...Roller, 37.4
5... Copper collector, 39... Lithium layer, 47... Metal sheet, 4
9...Metal lithium.

Claims (1)

[Claims] 1. A material metal selected from the group consisting of lithium, lithium alloys, and lithium mixed with foreign substances, and whose melting point does not differ by more than ±50°C from the melting point of lithium, and has a certain thickness. A method of manufacturing a thin film electrode supported on a sheet of an electron conductive material using a roll of a sheet of an electron conductive material and a material supplied from a source of the material metal in order to make an electrode having a thin film of the material metal. A bath in which metal is in a molten state is provided and kept in an inert atmosphere, and while the sheet is continuously unrolled, a certain amount of the material metal in a molten state is continuously applied onto at least one of its two sides. hand,
A thin film with a constant thickness of about 0.1 to about 40 μm and a uniform surface is formed on the sheet, and the material metal in a molten state immediately solidifies when it comes into contact with the sheet. A method for manufacturing a thin film electrode supported on an electronically conductive material sheet, characterized in that the material metal is solidified in a controlled manner after forming the above-mentioned thin film on the sheet. 2. The sheet is made of metal, alloy, metallized glass fiber,
The method of claim 1, comprising a material selected from the group consisting of charged plastics and metallized plastics. 3. The method of claim 2, wherein said sheet is made of a metal selected from the group consisting of copper, nickel, iron, and molybdenum. 4. A method according to claim 2, characterized in that the sheet is an alloy of nickel, copper or iron. 5. The method of claim 4, wherein said sheet is made of brass, bronze, steel or Monel alloy. 6. The method of claim 2, wherein the sheet is made of nickel. 7. The method according to claim 6, wherein the material metal is metallic lithium. 8. The method according to claim 1, wherein the raw metal is a lithium alloy. 9. Lithium is antimony, bismuth, boron, tin,
2. The method according to claim 1, which is alloyed with or contains silicon and magnesium as extraneous substances. 10. A method according to claim 7, characterized in that the temperature of the bath is maintained at a temperature between the melting point of lithium and about 400°C. 11. The method of claim 10, characterized in that the sheet is unrolled on a molten lithium bath. 12. The method of claim 11, characterized in that the molten lithium applicator is continuously rotated in the molten lithium bath to maintain contact with the surface of the nickel sheet. 13. The axis of the roller of the applicator is parallel to the surface of the molten lithium, the bottom of the roller is spread in the molten lithium, while the top is in contact with the surface, and the surface of the roller is roughened. 13. A method according to claim 12, characterized in that the molten lithium is covered and transferred uniformly onto said side of the nickel sheet. 14. The rough surface is created by a regular geometric pattern,
14. The method of claim 13, wherein the pattern forms regularly spread recesses in the roller surface, the recesses storing molten lithium and transferring it onto the metal sheet. 15. The method of claim 14, wherein the size of the recess is determined as a function of the layer of pure lithium, lithium alloy or lithium containing foreign material. 16. The method according to claim 15, characterized in that the sheet is spread at a speed of 16.0.5 to 100 cm/s. 17. Before applying molten lithium to the sheet surface,
16. A method according to claim 15, characterized in that the roller is heated to prevent immediate solidification on the roller. 18. The method of claim 1, wherein the sheet is heat treated before and after applying the raw metal in a molten state to the sheet. 19. After coating the metal sheet with molten lithium, the surface is treated with a scraper to reduce the thickness of the applied lithium and, if necessary, to remove surface imperfections created by the rollers. 15. The method described in 15. 20. Process according to claim 15, characterized in that the lithium bath and the sheet near it are kept under an inert atmosphere free of oxygen and water vapor. 21. The method of claim 13, further comprising a scraper to remove excess molten material adhering to the surface of the roller before it is applied to the metal sheet to be coated. 22. In the supported thin film electrode, at least partially a layer of a material metal selected from the group consisting of lithium, lithium alloy, and lithium mixed with a foreign substance and whose melting point is within 50 ° C. of the melting point of lithium. an electronically conductive sheet coated on one side, the layer of base metal having a uniform thickness between about 0.1 and about 40 microns;
The surface of the layer is virtually smooth and has no irregularities,
A supported thin film electrode comprising an electronically conductive sheet that cannot be peeled off from the sheet using a knife when prepared by the method of claim 1. 3. The electrode of claim 22, wherein the sheet is made of a material selected from the group consisting of metals, metal alloys, metallized glass fibers, charged plastics, and metallized plastics. 4. Electrode according to claim 23, characterized in that the sheet is made of a metal selected from the group consisting of copper, nickel, iron and molybdenum. 5. The electrode according to claim 23, wherein the sheet is made of nickel, copper, or an alloy whose main component is iron. 6. An electrode according to claim 25, wherein the sheet is made of brass, bronze, steel or a solenoid alloy. 27. The electrode of claim 23, wherein the sheet is made of nickel. 28. The electrode according to claim 27, wherein the material metal is metallic lithium. 29. Claim 2, wherein the material metal is selected from lithium alloys.
2. The electrode according to 2. 30. The electrode of claim 29, wherein lithium is alloyed with antimony, bismuth, boron, tin, silicon, and magnesium. 31. An electrochemical generator consisting of an anode, a cathode and an electrolyte, wherein the anode is defined in any one of claims 22, 23 and 24. 32. An electrochemical generator consisting of an anode, a cathode and an electrolyte, wherein the anode is defined in any one of claims 25, 28 and 27. 33. An electrochemical generator consisting of an anode, a cathode and an electrolyte, wherein the anode is defined in either claim 29 or 30.